Light sensitive color photographic material

ABSTRACT

A light-sensitive silver halide color photographic material comprising one or more layers. At least one layer constituting the photographic material contains a dispersion in a difficulty water-soluble high boiling organic solvent, either singly or in admixture with a low boiling organic solvent, of two or more compounds represented by the general formula   WHEREIN R1, R2 and R3 are individually a hydrogen or halogen atom or a cycloalkyl, alkoxy, aryl, carbalkoxy or alkylsulfone group having one to six carbon atoms and at least one of the groups R1, R2 and R3 is not hydrogen; R4 and R5 are individually a hydrogen or halogen atom or an alkyl, cycloalkyl, alkoxy, aryl, carbalkoxy or alkylsulfone group having one to six carbon atoms; and the sum of the carbon atoms of R1, R2 and R3 is 8 or less, provided that in case the sum of the carbon atoms of R1 R2 and R3 is 8, each of R1, R2 and R3 has less than four carbon atoms.

imited States Patent 1 Kuwahara et al.

[ LIGHT-SENSITIVE COLOR PHOTOGRAPHIC MATERIAL [75] Inventors: YoshimiKuwabara, Koganei-shi,

Tokyo; Shunji Matsuo, Nishitama-gun, Tokyo; Hidehiko Ishikawa,Odawara-shi, Kanagawa-ken; Mikio Sato, Odawara-shi, Kanagawa-ken, all ofJapan [73] Assignee: Konishiroku Photo Industry Co.,

Ltd., Tokyo, Japan [22] Filed: May 23, 1972 [21] Appl. No.: 256,011

Related U.S. Application Data [63] Continuation of Ser. No. 889,298,Dec. 30, 1969 Primary Examiner-Ronald H. Smith Attorney-Waters, Roditi,Schwartz & Nissen June 12, 1973 [57] ABSTRACT A light-sensitive silverhalide color photographic mate rial comprising one or more layers. Atleast one layer constituting the photographic material contains adispersion in a difficulty watensoluble high boiling organic solvent,either singly or in admixture with a low boiling organic solvent, of twoor more compounds represented by the general formula N 2 R5 Ra wherein RR and R are individually a hydrogen or halogen atom or a cycloalkyl,alkoxy, aryl, carbalkoxy or alkylsulfone group having one to six carbonatoms and at least one of the groups R R and R is not hydrogen; R and Rare individually a hydrogen or halogen atom or an alkyl, cycloakyl,alkoxy, aryl, carbalkoxy or alkylsulfone group having one to six carbonatoms; and the sum of the carbon atoms of R R and R is 8 or less,provided that in case the sum of the carbon atoms of R R and R is 8,each of R R and R has less than four carbon atoms.

5 Claims, No Drawings 1 LIGHT-SENSITIVE COLOR PHOTOGRAPHIC MATERIALCROSS RELATED APPLICATION This application is a continuation ofapplication Ser. No. 889,298 filed Dec. 30, 1969 and now abandoned.

The present invention relates to light-sensitive color photographicmaterials containing ultraviolet ray absorbers. More particularly, theinvention pertains to light-sensitive color photographic materialshaving incorporated in at least one of the layers constituting thephotographic materials a solvent dispersion containing two or morecompounds represented by the general formula wherein R R and R areindividually a hydrogen or halogen atom or cycloalkyl, alkoxy, aryl,carbalkoxy or alkylsulfone group having one to six carbon atoms, and atleast one of said R R and R is not hydrogen; R and R are individually ahydrogen or halogen atom or an alkyl, cycloakyl, alkoxy, aryl,carbalkoxy or alkylsulfone group having one to six carbon atoms; and thesum of the carbon atoms of R R and R is 8 or less, provided that in casethe sum of the carbon atoms of R,, R, and R is 8, each of R R and R;,has less than four carbon atoms.

It is well known that ultraviolet rays have detrimental effects onphotographic images. Particularly in the case of a light-sensitive colorphotographic material which forms, by color development, a dye image onits lightsensitive emulsion layer, the said dye image is unstable toultraviolet rays and hence is liable to be decolored or discolored whensubjected to the action of ultraviolet rays. Further, there is the fearthat after formation of said dye image, a coupler remaining in thelightsensitive emulsion layer of the color photographic material bringsabout, due to the action of ultraviolet rays, a cause for contaminationof the dye image.

In order to protect photographic images from such action of ultravioletrays, various processes have been proposed heretofore. Among these, themost common porcess is such that a ultraviolet ray absorber isincorporated into a layer constituting a light-sensitive photographicmaterial, e.g. silver halide emulsion layer, protective layer, interlayer or the like. However, lightsensitive photographic materialsaccording to the prior art processes are not satisfactory in protectionof photographic images from ultraviolet rays, and have such drawbacksthat they are inferior in photographic properties or become unstable inproperties when stored for a long period of time.

In view of such circumstances as mentioned above, the present inventorsmade various studies for years to find that a light-sensitive colorphotographic material, which is obtained by incorporating an organicsolvent dispersion containing two or more compounds represented by theaforesaid general formula into at least one of the layers constitutingthe light-sensitive phogographic material, is markedly excellent inprotection of the photographic image from ultraviolet rays and isstorage stable for a long period of time without being deteriorated inphotographic properties.

The compounds represented by the aforesaid general formula are excellentultraviolet ray-absorbing agents when effectively absorb ultravioletrays without absorbing visible rays, are substantially colorless, andare so stable to ultraviolet rays that they are not injured inphotographic properties or contaminated even when irradiated withultraviolet rays. However, such excellent characteristics are notexhibited if said compounds are incorporated into layers constituting alightsensitive photographic material by the Fischers method (a methodcarried out by introducing a soluble group such as carboxyl or sulfonegroup into a ultravio let ray-absorbing agent, which has been madenondiffusible, to form a water-soluble alkali metal salt thereof andthen incorporating said alkali metal salt in a hydrophilic colloidlayer). Further, if only one compound represented by the aforesaidgeneral formula is applied to a light-sensitive photographic material byadoption of the solvent dispersion method (a method carried out in sucha manner that a non-diffusible ultraviolet ray-absorbing agent having anoleophilic group is dissolved in an organic solvent and is immediatelydispersed in an aqueous gelatine solution), crystals of said compounddeposit to greatly injure the photographic properties of the material,because the compounds of the aforesaid general formula are extremely lowin solubility in organic solvents. If, in the above case, the amount ofthe solvent is so increased as not to deposit the crystals of thecompound, a large amount of the organic solvent is necessarilyincorporated into the layers constituting the photographic material,whereby the penetration of other treating liquids into said layers isinhibited or physical properties of said layers are undesirablydeteriorated.

In contrast thereto, when two or more of the compounds represented bythe aforesaid general formula are subjected, according to the presentinvention, to the solvent dispersion method, the compounds show markedlyexcellent solubility for the organic solvent employed in said method, asis clear from the test Example set forth later. This has not beenanticipatable heretofore.

Typical examples of the compounds represented by the aforesaid generalformula, which are used in the present invention, are set forth belowtogether with the absorption maximum wave lengths thereof in methanol()t,,,,,,9"), but it is needless to say that compounds usable in thepresent invention are not limited thereto. 1.2-(2-I-Iydroxyphenyl-5'-t-butoxyphenyl)- benzotriazole k 335 my.

2. 2-(2'-I-Iydroxy-5'-ethoxyphenyl)-benzotriazole k 338 my.

3. 2-( 2'-I-Iydroxy-5 -methoxyphenyl )-benzotriazole h 350 mp.

4. 2-(2-Hydroxy-5 '-cyclohexoxyphenyl)-benzotriaz o1e h 340 mp.

2-(2'-Hydroxy-5'-phenylpheny1)- methoxybenzotriazole h 340 mp. 6.2-(2'-Hydroxy-5'-cyclohexylphenyl)-benzotriazole A 338 my 7.2-(2'-Hydroxy-5'-phenylphenyl)-benzotriazole h 340 my.

3 8. 2-(2-Hydroxy-5 '-methoxyphenyl)-5,6-dimethylbenzotriazole k 342 mp.

2-(2'-Hydroxy-5'-methoxyphenyl)-5- methylbenzotriazole k 350 mp.

10. 2-(2-l-Iydroxy-5'-phenylphenyl)-5- butoxybenzotriazole k 345 mu 1 1.2-(2'-Hydroxy-5 -methyoxyphenyl)-benzotriazole- S-ethylsulfone h 350 my.

12. t-Butyl-2-( 2'-hydroxy-5 '-methoxyphenyl)-benzotriazole-S-carboxylate k 340 my.

13. 2-(2'-Hydroxy-5 '-ch1orophenyl)-5- chlorobenzotriazole k 335 m .tl4. 2-( 2-Hydroxy-5 '-phenylphenyl)-S- chlorobenzotriazole k 342 my.

15. 2-( 2'-Hydroxy-5 '-cyclohexylphenyl)-5- chlorobenzotriazole k 342my. l6. 2-(2-Hydroxy-4, 5 '-dichlorophenyl )-benzotriazole k 334 mp,

17. t-Butyl 2-(2'-hydroxy-5 '-ethoxyphenyl)- benzotriazole-S-carboxylate18. 2-(2-l-Iydroxy3 ',5 dichlorophenyl)-5- methoxybenzotriazole k 350my.

19. 2-( 2'-Hydroxy-4',5 '-dichlorophenyl)-5- methylbenzotriazole k 348mp.

20. tButyl-2-(2-hydroxy-4'-methoxyphenyl)- benzotriazole-S-carboxylate k347 mp.

21. 2-( 2-Hydroxy-4'-butoxyphenyl)-benzotriazole-5- ethylsulfone A 351mp.

The following test example shows the fact that when two or more of theabove-mentioned compounds are used in combination, they interact eachother to exhibit markedly excellent solubility in organic solvents.

TEST EXAMPLE Two or more of the compounds represented by the aforesaidgeneral formula were mixed with each other in the proportions as shownin Table l, and the mixture was dissolved at 65C. in a mixed solventcomprising 1 ml. of tri-o-cresyl phosphate and 2 ml. of ethyl acetateand was dispersed in 10 ml. ofa 5 percent gelatine solution containing0.1 g. of saponin. Thereafter, the dispersion was added to 100 m1. of asilver chlorobromide emulsion, was coated onto a photographic barytapaper, and was then dried to prepare a sample. Each sample prepared inthe above manner was microscopically observed in dispersed state of theultraviolet rayabsorbing agent to obtain the results as set forth in theright hand column of Table l.

The amounts of the tri-O-cresyl phosphate necessary for individualdisperson of the exemplified compounds (2), (9), (l8) and (19) were 7ml., 6.5 ml., 5 ml. and 4 ml., respectively. Further, the amount ofethyl acetate employed in the above case was 2 ml., and no influence ondispersibility was observed even when said amount was varied.

TABLE 1 Exemplified compound Depo- Run No. (2) (9) (l8) (l9) sition 1 L0Great 2 1.0 g Great 4 1.0 g Great 5 0.5 0.5 None 6 0.5 0.5 None 7 0.50.5 None 8 0.5 0.5 None 9 0.5 0.5 None 10 0.5 0.5 None 11 0.33 0.33 0.33None 12 0.33 0.33 0.33 None 13 0.33 0.33 0.33 None [4 0.33 0.33 0.33None 15 0.25 0.25 0.25 0.25 None From the above test example, it isclear that when used in combination of two or more in accordance withthe present invention, the compounds represented by the aforesaidgeneral formula, which have substituents less in molecular weight inview of the fundamental structure for ultraviolet ray-absorbingcharacteristics, are greatly increased in solubility in organic solventsemployed in the solvent dispersion method to make it possible to attainsuccessfully far higher ultraviolet rayabsorbing efficiencies than thoseof the conventional ultraviolet ray-absorbing agents. Accordingly, thelightsensitive color photograhpic materials in accordance with thepresent invention have such advantages that the dye images obtained aregreatly inhibited from decoloration, discoloration or contamination dueto irradiation of ultraviolet rays, and are not colored or contaminatedby the ultraviolet ray-absorbing agents themselves. Further, they arefree from the fear that the photographic properties thereof would beinjured, because of the decrease in amount of organic solvents dispersedin layers of the photographic materials, and stably maintain excellentphotographic properties.

When specifically used in combination, the ultraviolet ray-absorbingagents employed in the present invention become soluble in a markedlysmall amount of organic solvent, as mentioned above. Accordingly, theincorporation of said agents into layers of lightsensitive photographicmaterials may be effected according to the conventional solventdispersion method, whereby they can be dispersed uniformly and stably ina finely-divided non-crystalline form into any one of the layersconstituting light-sensitive photographic materials. For example, theremay be adopted such procedures that a mixture of two or more membersselected from the above-mentioned ultraviolet ray-absorbing agents isdissolved in an organic solvent employed in the solvent dispersionmethod and is then dispersed in an aqueous gelatine solution by use of asuitable mixing means, and the resulting dispersion, when desired to beadded to a silver halide emulsion, is added thereto after completion ofthe second ripening, and when desired to be incorporated into anauxiliary layer, e.g. a protective layer or an inter layer, is added toa coating liquid which is the component of said layer. As the coatingliquids which are the components of the silver halide emulsion layer andauxiliary layers constituting lightsensitive photographic materials,there may be used those which have been employed heretofore, and theultraviolet ray-absorbing agents used in the present invention do notshow any detrimental interactions with with various photographicadditives present in said coating liquids. Further, the organic solventsolutions of the above-mentioned ultraviolet ray-absorbing agents may beincorporated with couplers, contamination-preventing agents, fluorescentwhitening agents, etc. Ordinarily; the total amount of theultraviolet-rayabsorbing agents is preferably 1-10 mg per 100 cm of thearea to be coated. In the above case, the mixing proportions of theultraviolet ray-absorbing agents used in combination are equalproportions. However, the mixing proportions are, of course, not limitedthereto and are variable according to the object of application.

The amount of organic solvent necessary for dispersing 1 g. of a mixtureof the ultraviolet ray-absorbing agents is adequately about 0.5 ml. to 3ml., though the amount varies depending on the combination and mixingproportions of the ultraviolet ray-absorbing agents employed and on thekind of the organic solvent. The organic solvent employed in the abovecase may be any of those which have heretofore been used in the solventdispersion method. For example, there is used a difficultywater-miscible high boiling solvent having a boiling point of more than150C. such as di-n-butyl phthalate, triphenyl phosphate, tri-o-cresylphosphate or the like, either singly or in combination with a lowboiling solvent such as methyl acetate, ethyl acetate, propyl acetate,n-butyl acetate, ethyl propionate, carbon tetrachloride, chloroform,methanol, ethanol, dimethylformamide, dioxane, methyl cellosolve acetateor the like.

The light-sensitive color photographic materials of the presentinvention, which are produced in the above-mentioned manner, have suchadvantages that the ultraviolet ray-absorbing agents contained thereindo not crystallize and deposit during the production and storage of thephotographic materials and photographic properties can be stablymaintained even when they are irradiated with ultraviolet rays.

The present invention is illu'stated in detail below with reference toexamples.

EXAMPLE 1 Onto a photographic baryta paper was applied a redcolor-sensitive silver chlorobromide gelatine emulsion containing a cyancoupler. Thereafter, a gelatine protective layer containing one or moreof the exemplified compounds (2), (9), 18) and (19) in such proportionsas set forth in Table 2 was applied so that the amount of theultraviolet ray-absorbing agent became 2.8 ing/100 cm, followed bydrying. 1n the above manner, there were prepared samples 1-9 of whichsample 1 was a so-called blank sample containing no ultravioletray-absorbing agent.

In the application of the above-mentioned gelatine protective layer,there was used a liquid formed by dissolving at 65C. 3 parts of theultraviolet ray-absorbing agent(s) in a mixed solvent comprising 6 partsof ethyl acetate and 3 parts of tri-o-cresyl phosphate, adding theresulting solution to 60 parts of a 10 percent aqueous gelatine solutioncontaining saponin, dispersing the mixed solution by means of a colloidmill and then adding 40-parts of water to the resulting dispersion.

The above-mentioned samples were exposed to light, were subjected tocolor development, stopping, film hardening-fixing, bleaching-fixing andwater-washing treatments, and were then dried. The red color densitiesof cyan images of these samples and the contamination densities(measured on the basis of blue color densities) of non-image portionsthereof were measured before and after exposure to direct sunlight for50 hours to calculate the red color density lowering ratios andcontamination densities of the samples. The results were as set forth inTable 3.

TABLE 2 Exemplified compound Sample Total No. (18) (19) amount FromTable 3, it is understood that in the case of samples 2-5 prepared byindependent use of the exemplified compounds (2), (9), 18) and (19), theultraviolet ray-absorbing agents had crystallized and deposited, andhence were lowered in ultraviolet rayabsorbing ability to inhibit onlyslightly the discoloration of color images and the generation ofcontamination. On the other hand, in the case of the samples 6-9 inaccordance with the present invention, the discoloration of cyan dyesand increase of contamination were greatly inhibited.

EXAMPLE 2 Onto a photographic baryta paper was applied a samplescolor-sensitive silver chlorobromide gelatine emulsion layer containinga magenta coupler, which layer had been incorporated according to thesame procedure as in Example 1 with a liquid containing one or more ofthe exemplified compounds (1), (8), (11) and (20) in such proportions asset forth in Table 4, so that the amount of the ultravioletray-absorbing agent(s) became 8.2 mg/lOO cm, followed by drying. In theabove manner, there were prepared samples l-8, of which sample 1 was ablank sample.

The green color densities of image portions of these samples and thecontamination densities (measured on the basis of blue color densities)of white grounds thereof were measured before and after exposure toFade-Ometer to calculate green color density lowering ratios andcontamination densities of the samples. The results were as set forth inTable 5.

Green color density lowering ration Sample Contamination density Beforetest After test From Table 5, it is understood that in the case of thesamples 6-8 in accordance with the present invention, the discolorationof magenta dye and the increase of contamination were greatly inhibited.

EXAMPLE 3 Onto a photographic baryta paper were applied a redcolor-sensitive silver chlorobromide emulsion layer containing a cyancoupler, and a green color-sensitive silver chlorobromide emulsion layercontaining a magenta coupler. Further, a gelatine inter layer containingone or more of the exemplified compounds (2), (7), (l5) and (21) in suchproportions as shown in Table 6 was applied thereon so that the amountof the ultraviolet ray-absorbing agent(s) became 0.4 mg/lOO cm. Inaddition, a blue color-sensitive silver chlorobromide emulsion layercontaining a yellow coupler, which layer had been incorporated with oneor more of the exemplified compounds (2), (7), (l5) and (21) in theproportions as shown in Table 6, was applied so that the amount of theultraviolet ray-absorbing agent(s) became 1.0 mg/lOO cm, and then agelatine protective layer was applied, followed by drying. In the abovemanner, there were prepared samples l-9, of which sample 1 was a blanksample.

The gelatine layer and the blue color-sensitive silver chlorobromideemulsion layer containing the exemplified compounds (2), (7), l5) and(21) in such proportions as shown in Table 6 were prepared individuallyby dissolving at 65C. 4 parts of one or more of the ultravioletray-absorbing agents in a mixed solvent comprising 3 parts of triphenylphosphate and 10 parts of butyl acetate, adding the resulting solutionto parts of a 10 percent solution containing saponin, dispersing themixed solution by means of an ultrasonic emulsifier, and then adding thedispersion to 40 parts of water or to 200 parts of a bluecolor-sensitive silver chlorobromide emulsion.

The above-mentioned samples 1-9 were exposed, were subjected to colordevelopment, stopping, film hardening, fixing, bleaching fixing andwater-washing treatments, and were then dried. The blue, green and redcolor densities of image portions of these samples and the contaminationdensities (measured on the basis of blue color densities) of whitegrounds thereof were measured before and after exposure to directsunlight for 6 hours to calculate individual color density loweringratios and contamination densities. The results were as set forth inTable 7.

TABLE 6 Exemplified compound Sample Total No. (2) (7) (15) (21) amount 9l 1 l l 4 TABLE 7 Density lowering ratio Sample Blue Green RedContamination density No. color color color Before After test test 1 4150 63 0.09 0.23 2 40 50 60 0.09 0.23 3 38 49 60 0.09 0.23 4 38 47 580.09 0.21 S 35 47 56 0.09 0.19 6 3 5 8 0.09 0.10 7 3 6 7 0.09 0.10 8 2 45 0.09 0.l1 9 l 4 8 0.09 0.09

As is clear from Table 7, the samples 6-9 in accordance with the presentinvention are markedly less in discoloration of individual colordensities and in increase of contamination.

What we claim is:

l. A light-sensitive silver halide color photographic materialcomprising one or more layers wherein at least one layer constitutingthe photographic material contains a dispersion in a difficultlywater-soluble high boiling organic solvent, either singly or inadmixture with a low boiling organic solvent, of 2 or more compoundsrepresented by the general formula wherein R1, R2 and R are individuallya hydrogen or halogen atom or a cycloalkyl, alkoxy, aryl, carbalkoxy oralkylsulfone group having one to six carbon atoms and at least one ofthe groups R R and R is not hydrogen; R and R are individually ahydrogen or halogen atom or an alkyl, cycloalkyl, alkoxy, aryl,carbalkoxy or alkylsulfone group having one to six carbon atoms; and thesum of the carbon atoms of R R and R is 8 or less, provided that in casethe sum of the carbon atoms of R R and R is 8, each of R R and R hasless than four carbon atoms.

2. A photographic material as in claim 1 whereein R is methoxy, ethoxy,n-butoxy, t-butoxy, phenyl, cyclohexyl or chloro, R,, R, and R arehydrogen or chloro and R is hydrogen, methyl, ethyl sulfonyl, chloro,methoxy, or carbo-r -butoxy.

3. A photographic material as claimed in claim 1 wherein said materialcomprises equal amounts of 2(2'- hydroxy-S-cyclohexoxyphenyl)benzotriazole and 2(2-hydroxy-5' tert-butoxyphenyl) benzotriazole.

4. A photographic material as claimed in claim 1 wherein said materialcomprises equal amounts of 2-(2-hydroxy-3',5'dichlorophenyl)-5-methoxybenzotriazole and2-(2-hydroxy-5'-phenylphenyl)-5- chlorobenzotriazole.

5. A photographic material as claimed in claim 1 wherein said materialcomprises equal amounts of 2-(2'-hydroxy-5'cyclohexoxyphenyl)-benzotriazole, 2(2'-hydroxy-5' tert-butoxyphenyl)benzotriazole, 2- (Z'hydroxy-S-phenylphenyl)-5-chlorobenzotriazole and2-( 2'-hydroxy-5 '-cyclohexoxyphenyl benzotriazole.

2. A photographic material as in claim 1 whereein R1 is methoxy, ethoxy,n-butoxy, t-butoxy, phenyl, cyclohexyl or chloro, R2, R3 and R5 arehydrogen or chloro and R4 is hydrogen, methyl, ethyl sulfonyl, chloro,methoxy, or carbo-t -butoxy.
 3. A photographic material as claimed inclaim 1 wherein said material comprises equal amounts of2(2''-hydroxy-5-cyclohexoxyphenyl) benzotriazole and 2(2''-hydroxy-5''tert-butoxyphenyl) benzotriazole.
 4. A photographic material as claimedin claim 1 wherein said material comprises equal amounts of2-(2''-hydroxy-3'',5'' -dichlorophenyl)-5-methoxy-benzotriazole and2-(2''-hydroxy-5''-phenylphenyl)-5-chlorobenzotriazole.
 5. Aphotographic material as claimed in claim 1 wherein said materialcomprises equal amounts of 2-(2''-hydroxy-5''-cyclohexoxyphenyl)-benzotriazole, 2(2''-hydroxy-5'' tert-butoxyphenyl)benzotriazole, 2-(2''hydroxy-5''-phenylphenyl)-5-chlorobenzotriazole and2-(2''-hydroxy-5''-cyclohexoxyphenyl)-benzotriazole.